X-ray Diffraction

The Basics Followed by a few examples of Data Analysis by Wesley Tennyson

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X-ray Diffraction
Braggs Law Lattice Constants Laue Conditions - 2 Scan Scherrers Formula Data Analysis Examples

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Braggs Law
n = 2 d sin Constructive interference only occurs for certain s correlating to a (hkl) plane, specifically when the path difference is equal to n wavelengths.

Bragg conditions
The diffraction condition can be written in vector form 2kG + G2 = 0 k - is the incident wave vector k - is the reflected wave vector G - is a reciprocal lattice vector such that where G = k = k - k the diffraction condition is met

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Lattice Constants
The distance between planes of atoms is d(hkl) = 2 / |G| Since G can be written as G = 2/a (h*b1+ k*b2 +l*b3) Substitute in G d(hkl) = a / (h2 + k2 + l2)(1/2) Or a = d * (h2 + k2 + l2)(1/2) a is the spacing between nearest neighbors
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Laue Conditions
a1k = 21 a2k = 22 a3k = 23
Each of the above describes a cone in reciprocal space about the lattice vectors a1, a2, and a3. the i are integers When a reciprocal lattice point intersects this cone the diffraction condition is met, this is generally called the Ewald sphere.
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Summary of Bragg & Laue

When a diffraction condition is met there can be a reflected X-ray

Extra atoms in the basis can suppress reflections

n d 2 sin

Three variables , , and d is known is measured in the experiment (2) d is calculated

a d h k l
2 2

From the planes (hkl)

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a is calculated

 - 2 Scan
The - 2 scan maintains these angles with the sample, detector and X-ray source
Normal to surface

Only planes of atoms that share this normal will be seen in the - 2 Scan
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 - 2 Scan
The incident X-rays may reflect in many directions but will only be measured at one location so we will require that:

Angle of incidence (i) = Angle of reflection (r)

This is done by moving the detector twice as fast in as the source. So, only where i = r is the intensity of the reflect wave (counts of photons) measured.
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 - 2 Scan

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Smaller Crystals Produce Broader XRD Peaks

Scherrers Formula
K t B cos B
t = thickness of crystallite K = constant dependent on crystallite shape (0.89) = x-ray wavelength B = FWHM (full width at half max) or integral breadth B = Bragg Angle

Scherrers Formula
What is B? B = (2 High) (2 Low) B is the difference in angles at half max
Peak

2 low

2 high

Noise

When to Use Scherrers Formula

Crystallite size <1000 Peak broadening by other factors

Causes of broadening
Size Strain Instrument

If breadth consistent for each peak then assured broadening due to crystallite size

K depends on definition of t and B Within 20%-30% accuracy at best

Sherrers Formula References Corman, D. Scherrers Formula: Using XRD to Determine Average Diameter of Nanocrystals.

Data Analysis
the data (2 vs. Counts) Determine the Bragg Angles for the peaks Calculate d and a for each peak Apply Scherrers Formula to the peaks
Plot

Bragg Example

Bragg Example
d = / (2 Sin B) = 1.54 = 1.54 / ( 2 * Sin ( 38.3 / 2 ) ) = 2.35 Simple Right!

Scherrers Example
Au Foil
10000 9000

8000 98.25 (400) 7000

6000

Counts

5000

4000

3000

2000

1000

0 95 95.5 96 96.5 97 97.5 98 98.5 2 Theta 99 99.5 100 100.5 101 101.5 102

Scherrers Example
0.89 t B cos B
t = 0.89* / (B Cos B) = 1200 = 1.54
= 0.89*1.54 / ( 0.00174 * Cos (98.25/ 2 ) )

B = (98.3 - 98.2)*/180 = 0.00174

Simple Right!